CN108134097B - Preparation method of perovskite type cathode for low-temperature solid fuel cell - Google Patents
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Abstract
The invention provides a preparation method of a perovskite type cathode for a low-temperature solid fuel cell, which comprises the steps of mixing and stirring metal nitrate, alkali metal and oxides thereof with auxiliary agents such as a precipitator, a complexing agent, a dispersing agent and the like uniformly to obtain an ABO3 perovskite type precursor, mixing the precursor with cerium oxide and silicon oxide, then sintering at high temperature to obtain a Doped Cerium Oxide (DCO)/perovskite type powder material, carrying out treatment through a ball milling planetary mill and the like to reduce the particle size of the powder, and preparing the powder into a membrane electrode through a tape casting method. The A metal is La series, the B metal is transition metal, the precipitator is ammonia water, ammonium carbonate, urea and the like, the complexing agent is citric acid, and the dispersing agent is polyacrylonitrile organic solvent. The invention solves the problems of membrane electrode cracking, wrinkling and the like caused by the thermal expansion coefficient of the traditional perovskite cathode and cerium oxide electrolyte in the working process of the battery, reduces the internal resistance change caused by thermal expansion and prolongs the service life of the membrane electrode.
Description
Technical Field
The invention belongs to the field of fuel cell cathode preparation, and particularly relates to a preparation method of a perovskite cathode for a low-temperature solid fuel cell.
Background
A fuel cell is a power generation device that directly converts chemical energy of a fuel and an oxidant into electrical energy through an electrochemical reaction. Mainly comprises a positive electrode, a negative electrode, electrolyte and auxiliary equipment. The principle of the fuel cell is an electrochemical device, and the composition of the fuel cell is the same as that of a general battery. The single cell is composed of a positive electrode and a negative electrode (a negative electrode, namely a fuel electrode, and a positive electrode, namely an oxidant electrode) and an electrolyte. Except that the active material of a general battery is stored inside the battery, and thus, the battery capacity is limited. The positive and negative electrodes of the fuel cell do not contain active materials themselves, but are catalytic conversion elements. Fuel cells are thus well-known energy conversion machines that convert chemical energy into electrical energy. When the cell is operated, the fuel and the oxidant are supplied from the outside to react. In principle, the fuel cell can generate electricity continuously as long as reactants are continuously fed and reaction products are continuously discharged. Common fuels include, in addition to hydrogen, methanol, hydrazine, hydrocarbons, carbon monoxide, and the like. The oxidant is typically oxygen or air. Common electrolytes include phosphoric acid, potassium hydroxide, molten carbonate, ion exchange membranes, and the like. And a power generation device for directly converting chemical energy of the fuel and the oxidant into electric energy through an electrochemical reaction. Fuel cells can theoretically be operated at thermal efficiencies approaching 100% with high economy. Currently, due to the limitation of various technical factors, the total conversion efficiency of various fuel cells in actual operation is more than 45% -60%, for example, the utilization of waste heat can reach more than 80%, considering the energy consumption of the whole device system. In addition, the fuel cell device has no or few moving parts, is reliable in operation, requires less maintenance, and is quieter than conventional generator sets. In addition, the electrochemical reaction is clean and complete, and harmful substances are rarely generated. All of this has led to the fuel cell being considered a promising energy source power plant.
The fuel cell is an electrochemical power generation device, isothermal and in an electrochemical mode, chemical energy is directly converted into electric energy without a heat engine process, and the limitation of Carnot cycle is avoided, so that the fuel cell has high energy conversion efficiency, is free from noise and pollution, and is becoming an ideal energy utilization mode. Meanwhile, as the fuel cell technology is continuously mature and sufficient natural gas sources are provided by the west-east gas transmission engineering, the commercial application of the fuel cell has wide development prospect. The main components of the fuel cell are: electrodes (electrodes), Electrolyte membranes (Electrolyte membranes), current collectors (current collectors), and the like.
The electrode of the fuel cell is an electrochemical reaction site where the fuel undergoes an oxidation reaction and the oxidant undergoes a reduction reaction, and the key to the performance of the fuel cell lies in the performance of the catalyst, the material of the electrode, the manufacturing process of the electrode, and the like. The electrode can be mainly divided into two parts, one part is an Anode (Anode), the other part is a Cathode (Cathode), and the thickness is generally 200-; the structure of the electrode is different from the plate electrode of a general battery in that the electrode of the fuel cell has a porous structure, so the main reason for designing the porous structure is that most of the fuel and oxidant used by the fuel cell are gases (such as oxygen, hydrogen, etc.), and the solubility of the gases in the electrolyte is not high, so in order to improve the actual working current density of the fuel cell and reduce the polarization, the electrode with the porous structure is developed to increase the surface area of the electrode participating in the reaction, which is one of the important key reasons that the fuel cell can be put into practical use from the theoretical research stage at first.
At present, the electrodes of high temperature fuel cells are mainly made of catalyst materials, such as Y2O 3-stabilized-ZrO 2 (YSZ) of Solid Oxide Fuel Cells (SOFC) and nickel oxide electrodes of Molten Carbonate Fuel Cells (MCFC), etc., while low temperature fuel cells are mainly composed of a thin layer of catalyst materials supported by a gas diffusion layer, such as platinum electrodes of Phosphoric Acid Fuel Cells (PAFC) and Proton Exchange Membrane Fuel Cells (PEMFC).
The primary function of the electrolyte membrane is to separate the oxidant and reductant and to conduct ions, so the thinner the electrolyte membrane is, the better, but also the strength is to be considered, which is typically about tens to hundreds of millimeters thick in terms of current technology; as for the material, at present, two main development directions are provided, one is to make a porous separator with an insulating material such as an Asbestos (Asbestos) film, a silicon carbide SiC film, a lithium aluminate (LiAlO 3) film, and the like, and then to immerse the porous separator in molten lithium-potassium carbonate, potassium hydroxide, phosphoric acid, and the like so as to attach the porous separator to the pores of the porous separator, and the other is to use a perfluorosulfonic acid resin (e.g., PEMFC) and YSZ (e.g., SOFC).
The current collector is also called Bipolar Plate (Bipolar Plate) and has the functions of collecting current, separating oxidant and reducing agent, and guiding reaction gas, and the performance of the current collector mainly depends on the material characteristics, flow field design and processing technology thereof.
At present, the working temperature of the solid oxide fuel cell is mainly concentrated at 600-1000 ℃, the perovskite cathode of the traditional low-temperature membrane electrode causes the internal resistance of the membrane electrode to be increased due to the mismatch of the thermal expansion coefficients of the electrolyte and the electrode layer at low temperature, and the membrane material is easy to crack, age and the like. Therefore, the method has important practical significance for improving the bonding energy and prolonging the service life of the perovskite/cerium oxide-based membrane electrode.
Disclosure of Invention
The invention aims to provide a preparation method of a perovskite cathode for a low-temperature solid fuel cell, which solves the problems of membrane electrode cracking, wrinkling and the like caused by thermal expansion coefficients of the traditional perovskite cathode and a cerium oxide electrolyte in the working process of the cell, reduces internal resistance change caused by thermal expansion, and prolongs the service life of the membrane electrode.
The invention relates to a specific technical scheme as follows:
a preparation method of perovskite type cathode for low-temperature solid fuel cell, using metal nitrate, alkali metal and its oxide to mix and stir with precipitator, complexing agent, dispersant evenly, obtain ABO3 type perovskite type precursor, then mix with cerium oxide, silicon oxide and then carry on the high-temperature sintering, obtain and mix cerium oxide/perovskite type powder material, reduce the particle size of the powder through the ball-milling planet grinding, prepare into membrane electrode through the tape casting method finally, its concrete step is as follows:
s01: adding a small amount of precipitator, complexing agent and dispersing agent into metal nitrate, alkali metal and alkali metal oxide with equal mass at the temperature of 150-200 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite type precursor;
s02: preserving the temperature of the ABO3 perovskite type precursor prepared in the step for 3-5 hours at the temperature of 150 ℃;
s03: after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at high temperature to obtain a doped cerium oxide/perovskite powder material;
s04: ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The perovskite type composite oxide ABO3 is a novel inorganic non-metallic material with unique physical and chemical properties, the A site is generally rare earth or alkaline earth element ions, the B site is transition element ions, and the A site and the B site can be partially replaced by other metal ions with similar radiuses to keep the crystal structure of the A site and the B site basically unchanged, so that the A site and the B site are theoretically ideal samples for researching the surface and catalytic properties of the catalyst. As the compound has stable crystal structure, unique electromagnetic property and high activities of oxidation reduction, hydrogenolysis, isomerization, electrocatalysis and the like, the compound has great development potential in the fields of environmental protection, industrial catalysis and the like as a novel functional material.
The perovskite composite oxide has a unique crystal structure, particularly a crystal defect structure and performance formed after doping, or can be applied to various fields such as solid fuel cells, solid electrolytes, sensors, high-temperature heating materials, solid resistors and redox catalysts for replacing noble metals, and becomes a research hotspot in the fields of chemistry, physics, materials and the like.
The doped cerium oxide is doped with the cerium oxide, the cerium oxide is yellowish and reddish, and is pink, and the cerium oxide can be used as a polishing material, a catalyst carrier (auxiliary agent), an ultraviolet absorbent, a fuel cell electrolyte, an automobile exhaust absorbent, electronic ceramics and the like; the invention selects cerium oxide doped perovskite, which can stimulate the catalytic performance of perovskite and reduce the thermal expansion coefficient of perovskite phase. And meanwhile, silicon oxide is doped, and the silicon oxide phase can reduce the sintering temperature and the thermal strain capacity of the membrane electrode in the working process of the cell while improving the bonding energy of perovskite and cerium oxide.
As a further improvement of this embodiment, the metal nitrate is a nitrate other than an alkali metal.
As a further improvement of the scheme, the sum of the mass of the precipitator, the complexing agent and the dispersing agent is not more than 3% of the total mass of the metal nitrate, the alkali metal and the alkali metal oxide.
The addition sequence of the precipitant, the complexing agent and the dispersing agent is that the complexing agent is firstly used, then the dispersing agent is added, and finally the precipitant is added, and the time interval between each step is at least 30 minutes.
Wherein the mass ratio of the precipitator to the complexing agent to the dispersing agent is 3: 1-2:1-2.
The complexing agent is a compound capable of forming a complex ion with a metal ion. In the electroplating solution, complexing agents are required for most electroplating solutions, such as alkaline solution silver plating, gold plating, copper plating, zinc plating, tin plating, copper-tin alloy plating and the like, except for a few electroplating solutions, such as acidic solution iron plating, nickel plating, chromium plating and copper plating, which do not use or need not use complexing agents. Such as cyanide, hydroxide, citrate, pyrophosphate, thiosulfate, sulfite, etc., are widely used as complexing agents in electroplating production.
The complexing agent selected in the invention is organic phosphonate, such as ethylene diamine tetra methylene sodium phosphate (EDTMPS), diethylenetriamine penta methylene phosphonate (DETPMS), amine trimethophorate and the like. The product has stronger chelating capacity than EDTA and phosphate, high complexing capacity, large complexing stability constant, less dissociation of complexed metal ion, high chemical stability and easy biodegradation. They have very good performances of complexation solubilization, Threshold effect, lattice distortion and the like, have certain dispersion and suspension forces, have functions of scale inhibition, corrosion inhibition and scale removal, do not lose activity at higher temperature (such as 200 ℃), are basically nontoxic and have no pollution.
After the metal ions are completely complexed, a dispersant is added, the dispersant used in the present invention is a metal salt of a higher fatty acid, known as a metal soap, such as barium stearate (batt); zinc stearate (ZnSt); calcium stearate; other soaps of stearic acid such as cadmium stearate (CdSt), magnesium stearate (MgSt), copper stearate (CuSt).
Finally, adding a precipitator, wherein the organic precipitator is selected, the organic precipitator and metal ions form precipitates with high selectivity, and the precipitates have the advantages of constant composition, large molar mass, low solubility, less adsorbed inorganic impurities and the like; organic precipitants generally form chelate precipitates or associate precipitates with the metal ions. Therefore, organic precipitants can be classified into two types, i.e., chelate-forming precipitants and associate-forming precipitants. The invention selects a precipitant for generating chelate, an organic precipitant capable of forming chelate sediment, and at least two groups. One is an acidic group, such as-OH, -COOH, -SH, -SO 3H, etc.; and the other is a basic group such as-NH 2, one NH-one, ═ N-one, ═ C ═ O and ═ C ═ S, etc. These functional groups have unshared electron pairs and can be coordinately bound to a metal to form a complex.
As a further improvement of the scheme, the mixing ratio of the cerium oxide and the silicon oxide is 1: 3.
As a further improvement of the scheme, the sum of the mass of the cerium oxide and the silicon oxide is not more than 30% of that of the ABO3 perovskite type precursor.
As a further improvement of the scheme, the temperature of the high-temperature sintering in the step S03 is 800-1000 ℃.
As a further improvement of the scheme, the particle size of the powder obtained by the treatment in the step S04 is between 0.3 and 1 mm.
Compared with the prior art, the invention has the outstanding characteristics and excellent effects that: the alkali metal is used for doping the perovskite and the cerium oxide to improve the oxygen vacancy concentration, simultaneously reduce the viscosity of a precursor, improve the surface tension of the film and reduce the thermal expansion coefficient of the perovskite phase. The silicon oxide phase can improve the bonding energy of perovskite and cerium oxide and simultaneously reduce the sintering temperature and the thermal strain capacity of the membrane electrode in the working process of the cell; the invention solves the problems of membrane electrode cracking, wrinkling and the like caused by the thermal expansion coefficient of the traditional perovskite cathode and cerium oxide electrolyte in the working process of the battery, reduces the internal resistance change caused by thermal expansion and prolongs the service life of the membrane electrode.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 150 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 3 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 800 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.3mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 2% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate ethylene diamine tetra methylene sodium phosphate (EDTMPS), the dispersing agent is barium stearate (BaSt), the using amount of the barium stearate is 0.5%, the precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is not more than 30% of that of an ABO3 type perovskite precursor.
Through experimental detection, the expansion coefficient of the finally prepared perovskite type cathode in a normal working state is 1.32.
Example 2
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metallic sodium and sodium oxide at 160 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 4 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 900 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.5mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 3% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate diethylenetriamine penta methylene phosphonate (DETPMS). The dispersant is zinc stearate (ZnSt) with the dosage of 0.3 percent, the precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 25 percent of that of the ABO3 perovskite precursor.
Through experimental detection, the expansion coefficient of the finally prepared perovskite type cathode in a normal working state is 1.29.
Example 3
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 170 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 5 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 1000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.6mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 3% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate amine trimethylene phosphate. The dispersing agent is calcium stearate, and the using amount of the calcium stearate is 0.2-1.5%; the precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 30% of that of the ABO3 perovskite type precursor.
Through experimental detection, the expansion coefficient of the finally prepared perovskite type cathode in a normal working state is 1.37.
Example 4
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metallic sodium and sodium oxide at 180 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 5 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 1000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 1mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 3% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate amine trimethylene phosphate. The dispersant is stearic acid soap such as cadmium stearate (CdSt), the precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 25% of that of the ABO3 perovskite type precursor.
Through experimental detection, the expansion coefficient of the finally prepared perovskite type cathode in a normal working state is 1.42.
Example 5
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 200 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 4 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at 9000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.8mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 3% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate diethylenetriamine penta methylene phosphonate (DETPMS). Magnesium stearate (MgSt) is selected as a dispersing agent, a precipitator for generating chelate is selected as a precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 28 percent of that of the ABO3 perovskite type precursor.
Through experimental detection, the expansion coefficient of the finally prepared perovskite type cathode in a normal working state is 1.43.
Example 6
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 180 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 3 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 1000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.9mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 1 percent of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate amine trimethylene phosphate. The dispersant is copper stearate (CuSt), the precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide to silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 20% of that of the ABO3 perovskite type precursor.
Through experimental detection, the expansion coefficient of the finally prepared perovskite type cathode in a normal working state is 1.47.
Comparative example 1
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 150 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 3 hours at the temperature of 150 ℃; ball milling and planetary milling at 500 deg.c to reduce the size of the powder to 0.3mm, and casting to prepare the membrane electrode.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 2% of the total amount of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate ethylene diamine tetra methylene sodium phosphate (EDTMPS), the dispersing agent is barium stearate (BaSt), the using amount of the barium stearate is 0.5%, and the precipitator is a chelate-forming precipitator.
Compared with the embodiment, the perovskite type cathode is different in that cerium oxide and silicon oxide are not doped, and the expansion coefficient of the perovskite type cathode in a normal working state is 1.12 through experimental detection.
Comparative example 2
Firstly, sequentially adding a small amount of dispersing agent and precipitating agent into calcium nitrate, metal sodium and sodium oxide with equal mass at 160 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 4 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 900 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.5mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator and the dispersing agent is 3% of the total amount of calcium nitrate, alkali metal and alkali metal oxide, wherein the dispersing agent is zinc stearate (ZnSt), the using amount of the zinc stearate is 0.3%, the precipitator is a precipitator for generating chelate, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 25% of that of the ABO3 perovskite type precursor.
Compared with the embodiment 2, the difference of the scheme is that no complexing agent is used, and the expansion coefficient of the finally prepared perovskite type cathode in the normal working state is 1.09 through experimental detection.
Comparative example 3
Firstly, sequentially adding a small amount of complexing agent and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 170 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 5 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 1000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.6mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator and the complexing agent is 3% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate amine trimethylene phosphate. The precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 30% of that of the ABO3 perovskite type precursor.
Compared with the embodiment 3, the difference of the scheme is that no dispersant is used, and the expansion coefficient of the finally prepared perovskite type cathode in the normal working state is 1.07 through experimental detection.
Comparative example 4
Firstly, sequentially adding a small amount of complexing agent and dispersing agent into equal mass of calcium nitrate, metal sodium and sodium oxide at 180 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 5 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 1000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 1mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the complexing agent and the dispersing agent is 3% of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate amine trimethylene phosphate. The dispersant is stearic acid soap such as cadmium stearate (CdSt); the mixing ratio of the cerium oxide and the silicon oxide is 1:3, and the sum of the mass of the cerium oxide and the mass of the silicon oxide is 25 percent of that of the ABO3 perovskite type precursor.
Compared with the embodiment 4, the difference of the scheme is that no precipitator is used, and the expansion coefficient of the finally prepared perovskite type cathode in the normal working state is 1.12 through experimental detection.
Comparative example 5
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into calcium nitrate at 200 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite type precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 4 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at 9000 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.8mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 3% of the total amount of calcium nitrate, wherein the complexing agent is organic phosphonate diethylenetriamine pentamethylene phosphonate (DETPMS). Magnesium stearate (MgSt) is selected as a dispersing agent, a precipitator for generating chelate is selected as a precipitator, the mixing ratio of cerium oxide and silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 28 percent of that of the ABO3 perovskite type precursor.
Compared with the embodiment 5, the difference of the scheme is that the perovskite type cathode is not doped with alkali metal and oxide thereof, and the expansion coefficient of the perovskite type cathode in the normal working state is 1.03 through experimental detection.
Comparative example 6
Firstly, sequentially adding a small amount of complexing agent, dispersant and precipitator into equal mass of calcium nitrate, metal potassium and potassium oxide at 180 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite precursor; then, the ABO3 perovskite type precursor prepared in the step is subjected to heat preservation for 3 hours at the temperature of 150 ℃; after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at the high temperature of 700 ℃ to obtain a doped cerium oxide/perovskite powder material; and finally, ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, wherein the particle size of the obtained powder is 0.9mm, and preparing the powder into a membrane electrode by a tape casting method after cooling.
The mass sum of the precipitator, the complexing agent and the dispersing agent is 1 percent of the total mass of calcium nitrate, alkali metal and alkali metal oxide, wherein the complexing agent is organic phosphonate amine trimethylene phosphate. The dispersant is copper stearate (CuSt), the precipitator is a chelate-generating precipitator, the mixing ratio of cerium oxide to silicon oxide is 1:3, and the mass sum of the cerium oxide and the silicon oxide is 20% of that of the ABO3 perovskite type precursor.
Compared with the embodiment 6, the difference of the scheme is that the sintering temperature is lower, and the expansion coefficient of the finally prepared perovskite type cathode in the normal working state is 1.27 through experimental detection.
Claims (6)
1. A preparation method of a perovskite cathode for a low-temperature solid fuel cell is characterized by comprising the following steps: the method comprises the following specific steps:
s01: adding a small amount of precipitator, complexing agent and dispersing agent into metal nitrate, alkali metal and alkali metal oxide with equal mass at the temperature of 150-200 ℃, and uniformly mixing and stirring to obtain an ABO3 perovskite type precursor; the metal nitrate is a nitrate other than an alkali metal;
s02: preserving the temperature of the ABO3 perovskite type precursor prepared in the step for 3-5 hours at the temperature of 150 ℃;
s03: after the heat preservation time is up, keeping the temperature unchanged, adding cerium oxide and silicon oxide, mixing, and then sintering at high temperature to obtain a doped cerium oxide/perovskite powder material;
s04: ball milling and planetary grinding the doped cerium oxide/perovskite powder material at the high temperature of 500 ℃ to reduce the particle size of the powder, and preparing the powder into a membrane electrode by a tape casting method after cooling.
2. The production method of a perovskite-type cathode for a low-temperature solid fuel cell according to claim 1, characterized in that: the sum of the mass of the precipitator, the complexing agent and the dispersing agent is not more than 3% of the total mass of the metal nitrate, the alkali metal and the alkali metal oxide; the mass ratio of the precipitator to the complexing agent to the dispersing agent is 3: 1-2:1-2.
3. The production method of a perovskite-type cathode for a low-temperature solid fuel cell according to claim 1, characterized in that: the mass ratio of the cerium oxide to the silicon oxide is 1: 3.
4. The production method of a perovskite-type cathode for a low-temperature solid fuel cell according to claim 3, characterized in that: the sum of the mass of the cerium oxide and the silicon oxide is not more than 30% of that of the ABO3 perovskite type precursor.
5. The production method of a perovskite-type cathode for a low-temperature solid fuel cell according to claim 4, characterized in that: the temperature of the high-temperature sintering in the step S03 is 800-1000 ℃.
6. The production method of a perovskite-type cathode for a low-temperature solid fuel cell according to claim 1, characterized in that: the particle size of the powder obtained by the treatment in the step S04 is between 0.3 and 1 mm.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006332027A (en) * | 2005-04-27 | 2006-12-07 | Tokyo Gas Co Ltd | Reformer-integrated fuel cell |
| CN103074124A (en) * | 2013-01-05 | 2013-05-01 | 大连理工大学 | Preparation method for nano-composite oxide heavy oil additive |
| CN103219525A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Low-temperature solid oxide fuel cell and making method thereof |
| CN103427094A (en) * | 2012-05-23 | 2013-12-04 | 中国科学院物理研究所 | Oxide with perovskite-type structure, preparation methods and applications |
| CN103826847A (en) * | 2011-09-21 | 2014-05-28 | 韩国电力公社 | Production method for a support type coating membrane using tape casting |
| CN104078687A (en) * | 2013-03-25 | 2014-10-01 | 中国科学院物理研究所 | Anode material containing alkali metal or alkaline-earth metal element of solid oxide fuel cell and preparation method and application thereof |
| CN105428664A (en) * | 2015-11-10 | 2016-03-23 | 辽宁石油化工大学 | Preparation method for electrode of solid oxide fuel cell |
| CN106328972A (en) * | 2016-08-29 | 2017-01-11 | 董晓 | Preparation method of mid-low temperature solid oxide fuel cell cathode material |
-
2017
- 2017-12-28 CN CN201711455780.9A patent/CN108134097B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006332027A (en) * | 2005-04-27 | 2006-12-07 | Tokyo Gas Co Ltd | Reformer-integrated fuel cell |
| CN103826847A (en) * | 2011-09-21 | 2014-05-28 | 韩国电力公社 | Production method for a support type coating membrane using tape casting |
| CN103219525A (en) * | 2012-01-19 | 2013-07-24 | 中国科学院上海硅酸盐研究所 | Low-temperature solid oxide fuel cell and making method thereof |
| CN103427094A (en) * | 2012-05-23 | 2013-12-04 | 中国科学院物理研究所 | Oxide with perovskite-type structure, preparation methods and applications |
| CN103074124A (en) * | 2013-01-05 | 2013-05-01 | 大连理工大学 | Preparation method for nano-composite oxide heavy oil additive |
| CN104078687A (en) * | 2013-03-25 | 2014-10-01 | 中国科学院物理研究所 | Anode material containing alkali metal or alkaline-earth metal element of solid oxide fuel cell and preparation method and application thereof |
| CN105428664A (en) * | 2015-11-10 | 2016-03-23 | 辽宁石油化工大学 | Preparation method for electrode of solid oxide fuel cell |
| CN106328972A (en) * | 2016-08-29 | 2017-01-11 | 董晓 | Preparation method of mid-low temperature solid oxide fuel cell cathode material |
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